Process and apparatus for reducing the nitrogen oxide content in exhaust gases by the controlled addition of NH3

ABSTRACT

In the reduction of quantities of No x  in the exhaust gases of lean bum engines such as diesel engines, using a selective reduction catalyst and a source of ammonia, the present invention improves overall conversion by supplying ammonia or a precursor intermittently so that it is adsorbed and desorbed during the engine operating cycle.

This application is the U.S. national-phase application of PCT International Application No. PCT/GB99/01205.

This invention concerns combatting air pollution from the exhaust gas of a lean burn engine. In particular, it concerns apparatus for, and a method of, reducing the content of nitrogen oxides (NOx) in such gas.

Lean burn engines (which have an air-fuel ratio greater than 14.7, generally in the range 19-50) exhibit higher fuel economy and lower hydrocarbon emissions than do stoichiometrically operated engines and are increasing in number. Emissions from diesel engines are now being regulated by legislation, and whilst it is not too difficult to meet regulations on hydrocarbon or CO emissions, it is difficult to meet regulations on NOx emissions. Since exhaust gas from lean burn engines such as diesel engines is high in oxygen content throughout the engine cycle, it is more difficult to reduce NOx to nitrogen than in the case of stoichiometrically operated engines. The difficulty is compounded by the lower gas temperature. Various approaches are being considered to reduce NOx under the oxidising conditions. One approach is that of selective catalytic reduction (SCR) with hydrocarbon, but a catalyst of sufficient activity and durability to achieve the required conversion has not been found. Another approach is to adsorb the NOx by an adsorbent when the exhaust gas is lean (ie when there is a stoichiometric excess of oxygen) and release and reduce the adsorbed NOx when the exhaust gas is rich, the exhaust gas being made rich periodically. During the lean operation, NO is oxidised to NO₂ which can then react readily with the adsorbent surface to form nitrate. This approach, though, is constrained at low temperature by restricted ability to form NO₂ and by adsorbent regeneration and at high temperature by sulphur poisoning. Most adsorbents operate in a certain temperature window and are deactivated by sulphate formation. The approach of the present invention is that of SCR of NOx by NH₃. This approach has been applied to static diesel engines using a V₂O₅—TiO₂ type catalyst.

The application of NH₃ SCR technology to the control of NOx emission from lean burn vehicles, however, requires a suitable NH₃ supply strategy, especially at low temperature, for various reasons. The engine-out NOx varies with temperature, so the amount of NH₃ supplied must be well controlled as a function of the temperature to maintain the appropriate stoichiometry for the reaction; an insufficient supply of NH₃ results in inadequate NOx reduction, whilst an excess may cause NH₃ to slip past the catalyst Whilst at sufficiently high temperature, the catalyst can selectively oxidise that excess NH₃ to N₂, at low temperature, the unreacted NH₃ will be emitted as such. Even if the proper stoichiometry of NH₃ is provided, the catalyst may not be sufficiently active at low temperature to react all the NH₃ with the NOx. For example, FIG. 1 shows the reaction of NH₃ with NOx over a non-metallised zeolite as a function of temperature at a stoichiometry of 1:1 at an inlet concentration of 200 ppm. It can be seen that at temperatures below 300° C. the reduction does not proceed to any significant extent. Furthermore, it has been reported that the presence of excess NH₃ at low temperature could lead to the formation of NH₄NO₃ and (NH₄)₂SO₄. There is also evidence that the presence of excess gas phase NH₃ can inhibit the NH₃ SCR reaction over some catalysts at low temperature. Urea is usually the preferred form of storing NH₃ on a vehicle. Urea is readily available and is stable in water solution. However, it only hydrolyses readily to NH₃ at temperatures greater than 150° C., and may not be a suitable source of NH₃ at low temperature. Exhaust gas temperatures, though, vary over an engine cycle and for the average light duty diesel car a significant fraction of that cycle is at low temperature. Thus, the control of NOx at low temperature is a problem.

Methods have been suggested to mitigate this problem. For instance, U.S. Pat. No. 5,785,937, JP-A-07136465 and U.S. Pat. No. 4,963,332 all suggest the use of ammonia as a reductant to convert NO_(x) to nitrogen over a catalyst EP-A-0773354 also describes the use of ammonia to reduce NO_(x) to nitrogen. However, ammonia is synthesis in situ over a three-way catalyst during the rich burning phase of the engine and the supply of ammonia is triggered as a function of the stoichiometry of the fuel in terms of the fuel to air ratio not as a function of temperature.

The present invention provides an improved apparatus and method for reducing the content of NOx.

Accordingly, the invention provides an apparatus for reducing the content of nitrogen oxides (NO_(x)) in the exhaust gas of a lean burn engine, which apparatus comprises:

(a) an exhaust capable of allowing exhaust gases to flow therethrough;

(b) a selective catalytic reduction catalyst located in the flow-path of the exhaust gas and being capable of (i) catalysing the reduction of the NO_(x) by ammonia to nitrogen and (ii) adsorbing and desorbing ammonia during the engine cycle;

(c) means for supplying ammonia from an ammonia source to the catalyst; and

(d) switching means for intermittently supplying ammonia during an engine cycle thereby enabling (i) the catalyst to adsorb ammonia when ammonia supply is switched on and (ii) the adsorbed ammonia to react with NO_(x) when ammonia supply is switched off,

characterised in that the catalyst comprises a zeolite and the switching means is triggered on and off at pre-set temperature levels of the catalyst.

The invention provides also a method of reducing the content of nitrogen oxides (NOx) in the exhaust gas of a lean burn engine, which method comprises passing the exhaust gas over a selective catalytic reduction catalyst which catalyses the reduction of the NOx by ammonia to nitrogen and which adsorbs and desorbs ammonia during the engine cycle, ammonia being supplied intermittently to the catalyst during the engine cycle, the catalyst adsorbing ammonia during its supply and the ammonia which has been adsorbed reacting with the NOx when the ammonia is not supplied.

We have discovered that ammonia can be absorbed on a SCR catalyst and thereafter used in the NOx reduction when ammonia is not being supplied. It is an advantage to be able to achieve the NOx reduction while supplying the ammonia intermittently. In particular, the ammonia supply can be halted and yet NOx reduction occur when the temperature of the catalyst is low and supply would have the problems referred to above. The stored ammonia can be used as reductant for NOx over the same catalyst without the presence of gas phase NH₃.

The ammonia can be supplied without the exhaust gas so that the catalyst adsorbs the ammonia and then the exhaust gas passed over the catalyst for the NOx reduction to occur Preferably, however, the exhaust gas is passed continuously over the catalyst.

The invention uses adsorption and desorption characteristics of the required catalyst. A higher amount of NH₃ will be adsorbed, and hence be available for subsequent reaction, if adsorption is at a lower temperature at which the catalyst adsorbs less NH₃. Preferably NH₃ is adsorbed at a temperature at which a large amount is adsorbed; the temperature is preferably below that of maximum desorption. The temperature, however, is preferably above that at which any significant formation of ammonium salts occurs. FIG. 2 shows the desorption profile from zeolite ZSM5 (non-metallised) of NH₃ which had been pre-adsorbed at 100° C. It can be seen that at say 300° C. more NH₃ is retained, adsorbed, than at say 400° C., and that the temperature of maximum desorption is about 370° C. Bearing in mind that the desorption of NH₃ is endothermic, it can also be seen that if NH₃ were adsorbed at say 300° C. and then heated, NH₃ would be desorbed in accordance with the graph so that less would be available for subsequent reaction, while if NH₃ were adsorbed at the same temperature, 300° C., and cooled, NH₃ would not be desorbed so the adsorbed NH₃ would be available for subsequent reaction. NH₃ stored on the ZSM5 catalyst at 250° C. can effectively be used to reduce NOx at a temperature as low as 150° C. under exhaust conditions simulating those of a light duty diesel car. FIG. 3 shows the NH₃ uptake of ZSM5 catalyst (non-metallised) from a gas mixture containing 4.5% CO₂, 12% O₂, 4.5% H₂O, 200 ppm CO, 100 ppm C₃H₆, 20 ppm SO₂ and 200 ppm NH₃ with the balance N₂ at 250° C., and FIG. 4 shows the subsequent reaction of that adsorbed NH₃ with NOx at 150° C. It can be seen that significant amounts of NOx are reduced by the adsorbed NH₃ over a period of time and that as the stored NH₃ is being consumed, the reduction reaction declines with time. When the temperature rises in the engine cycle, however, NH₃ can be applied again, and hence adsorbed NH₃ replenished. Accordingly, the problem of applying NH₃ at low temperature can be overcome by halting its supply and using adsorbed NH₃. The amount of NH₃ adsorbed on a fixed weight of catalyst can be increased by including its partial pressure in the gas mixture. For example, Table 1 gives the amount of NH₃ adsorbed by a zeolite at 250° C. from a simulated gas mixture of differing NH₃ concentrations.

TABLE 1 NH₃ Adsorption as a Function of NH₃ Concentration Amount NH₃ NH₃ Concentration Adsorbed (ppm) (mmoles per g) 200 0.63 500 1.22 1000 1.48

The means to make the supply of ammonia intermittent during the engine cycle in the present apparatus can be a switch which switches the ammonia supply on and off dependent on the level of NOx conversion occurring over the SCR catalyst. Preferably, however, the means to make the supply of ammonia intermittent comprises a switch to switch on the means to supply the ammonia when the temperature of the catalyst rises above a set level (i) during the engine cycle, and to switch off the means to supply the ammonia when the temperature of the catalyst falls below a set level (ii). The set level (i) is preferably in the range 250-400° C., especially in the range 250-350° C. The set level (ii) is preferably in the range 200-250° C.

The ammonia can be supplied for instance 1-30 times per minute.

The source of ammonia and means to supply it from the source to the catalyst can be conventional. Compounds of ammonia as a solid or a solution in water are preferred. The compounds are preferably urea or ammonium carbamate. The means to supply the ammonia from the source to the catalyst can be a pipe through which it is injected into the exhaust gas up-stream of the catalyst. Thus, the present invention can be employed to provide a method of promoting the conversion of NOx under oxidising conditions in an exhaust fitted with a means of injecting NH₃ and a catalyst which adsorbs NH₃ during parts of the engine cycle in which the exhaust gas is sufficiently warmed for the hydrolysis of NH₃ precursor and injection of ammonia and ammonia is adsorbed by the catalyst for use as reductant for NOx during parts of the engine cycle in which the exhaust gas is cooler, without the need for the continuous injection of NH₃ into the exhaust gas.

It can be seen that the invention provides an exhaust system for an engine operating generally under lean conditions, which exhibits a higher exhaust gas temperature and a lower exhaust gas temperature, the lower exhaust gas temperature being inadequate for the effective hydrolysis of NH₃ precursor and injection of NH₃ (generally a temperature below 200° C.), and an NH₃ SCR catalyst arranged and constructed so that during the higher exhaust gas temperature parts of the engine cycle the catalyst adsorbs NH₃ and during the lower exhaust gas temperature parts of the engine cycle the adsorbed NH₃ is used as reductant for NOx.

The catalyst can be any which has the required characteristics of the present catalyst. The same material can both selectively catalyse the reduction and also adsorb and desorb the ammonia, and this is preferred. However, different materials in the catalyst can perform the two functions, one material catalysing and one material adsorbing and desorbing. When different materials are employed, they can be physically separate or, preferably, in admixture one with another. A zeolite can perform both functions or a zeolite can be employed which performs one function together with a different material, which may or may not be a zeolite, which performs the other function. The catalyst preferably comprises a zeolite. The zeolite can be metallised or non-metallised, and can have various silica-to-alumina ratios. Examples are metallised or non-metallised ZSM5, mordenite, γ zeolite and β zeolite. Preferred is ZSM5 or ion-exchanged or metal impregnated ZSM5 such as Cu/ZSM5. It may be desirable that the zeolite contains metal, especially Cu, Ce, Fe or Pt; this can improve the low temperature SCR activity. The zeolite can contain for instance 1-10% of metal by weight. The catalyst should have an appropriate structure, for instance in terms of pore size or surface acid sites, to trap and release NH₃.

The catalyst is preferably carried out on a support substrate, in particular a honeycomb monolith of the flow-through type. The monolith can be metal or ceramic. The substrate can be conventional.

Nitrogen oxide (NO) is usually the most abundant nitrogen oxide in an engine exhaust stream, but at lower temperatures the reaction of the adsorbed NH₃ on a zeolite catalyst occurs more readily with NO₂ than with NO. Accordingly it is often desirably to oxidise NO to NO₂ up-stream of the SCR catalyst, particularly at low temperature.

The present engine can b a diesel or petrol (gasoline) engine. The diesel engine can be a light duty or heavy duty diesel engine. The engine is preferably that of a vehicle.

The invention is illustrated by the accompanying drawings, which are graphs in which:

FIG. 1 shows NOx and NH₃ concentrations in simulated exhaust gas against temperature after treatment by zeolite ZSM5, the NH₃ being supplied continuously;

FIG. 2 shows the temperature programmed desorption (TPD) of NH₃ from ZSM5 which had been pre-adsorbed at 100° C., the graph showing, in arbitrary units, the concentration of ammonia in the gas against temperature;

FIG. 3 shows the NH₃ concentration in a full simulated exhaust gas mixture containing 4.5% CO₂, 12% O₂, 4.5% H₂O, 200 ppm CO, 100 ppm C₃H₆, 20 ppm SO₂ and 200 ppm NH₃ with the balance N₂ after passage over ZSM5 at 250° C. against time, and hence shows the NH₃ uptake by the zeolite;

FIG. 4 shows the NOx concentration remaining in simulated exhaust gas after passage over the zeolite containing adsorbed NH₃ resulting from the adsorption shown in FIG. 3 against time;

FIG. 5 shows the NOx concentration remaining in simulated exhaust gas containing 200 ppm NO, 200 ppm CO, 12% O₂ and 14% CO₂ with the balance N₂ after passage over ZSM5 with and without pre-adsorption of NH₃ against temperature;

FIG. 6 shows the corresponding effect to that shown in FIG. 5 of successive cycles of the NH₃ pre-adsorption followed by subjection to the simulated exhaust gas;

FIG. 7 corresponds to FIG. 5 but with the simulated exhaust gas containing also hydrocarbon;

FIG. 8 corresponds to FIG. 7 but with the simulated exhaust gas containing also H₂O and SO₂;

FIG. 9 corresponds to FIG. 5 but with the simulated exhaust gas containing NO₂ instead of NO;

FIG. 10 corresponds to FIG. 9 but with the simulated exhaust gas containing also hydrocarbon;

FIG. 11 corresponds to FIG. 10 but with the simulated exhaust gas containing also H₂O and SO₂;

FIG. 12 shows NOx concentration and temperature against time during part of an engine cycle;

FIG. 13 corresponds to FIG. 12 but shows the effect of intermittent supply of NH₃;

FIG. 14 shows the NOx concentration remaining in simulated exhaust gas after passage over Cu/ZSM5 with and without pre-adsorption of NH₃ against temperature; and

FIG. 15 shows the NOx concentration remaining in simulated exhaust gas which is that used in relation to FIG. 14 but containing also hydrocarbon, H₂O and SO₂, after passage over Cu/ZSM5 with pre-adsorption of NH₃ against temperature.

FIGS. 1-4 are discussed further hereinbefore, and FIGS. 5-15 hereinafter.

The invention is illustrated also by the following Examples.

EXAMPLE 1 Reaction of NO With Pre-adsorbed NH₃ Over Non-metallised ZSM5

This Example shows the effect of pre-adsorbing NH₃ at 250° C. on the conversion of NOx over a non-metallised zeolite in a simple gas mixture containing NOx, CO, CO₂ and O₂ during a light-off test from room temperature to 400° C. The gas stream containing NO (200 ppm), CO (200 ppm), O₂ (12%), CO₂ (14%) with the balance N₂ at a flow rate of 2 liters per minute was first passed over the non-metallised zeolite (0.4 g) from room temperature to 400° C. at a heating rate of 50° C. per minute and the NOx at the outlet measured. In a subsequent experiment, the catalyst temperature was first raised to 250° C. and 200 ppm NH₃ was added to the gas stream, the zeolite was exposed to that stream for 5 minutes and then the NH₃ switched off, and the catalyst was cooled to room temperature and the rapid light-off repeated. FIG. 5 shows the outlet NOx concentration for these experiments. It can be seen that in the case where NH₃ was not pre-adsorbed over the catalyst, some of the NOx is adsorbed on the zeolite at low temperature and is then subsequently released between 150° C. and 350° C., but that when NH₃ was pre-adsorbed on the zeolite, the zeolite did not adsorb a significant amount of NOx at low temperature. Furthermore, it can be seen that a decrease in the outlet NOx concentration occurs from 150° C. to 450° C. due to the reaction of the NOx with the pre-adsorbed NH₃. This effect of reacting the adsorbed NH₃ with the NOx can be repeated over successive cycles with NH₃ injection at 250° C. between each cycle, as is shown in FIG. 6.

We have also shown that even in the presence of other gaseous components such as hydrocarbon, H₂O and SO₂, the adsorption of NH₃ will readily occur on the zeolite and can be used to reduce NOx. For example, FIG. 7 shows the effect of adding 200 ppm C₃H₆ to the gas mixture in similar tests to those described above and FIG. 8 shows the effect of further addition of H₂O (10%) and SO₂ (20 ppm). It can be seen that in both cases NOx was reduced by the adsorbed NH₃.

EXAMPLE 2 Reaction of NO₂ With Pre-adsorbed NH₃ Over Non-metallised ZSM5

The selective catalytic reduction of NOx by NH₃ under oxidising conditions proceeds more rapidly at low temperature if NO₂ instead of NO is present. The present Example shows that NH₃ pre-adsorbed on a zeolite catalyst can be used to reduce NO₂ even at a temperature as low as 100° C. This was demonstrated by rapid light-off tests analogous to that described above in Example 1. In the first experiment, a simple gas mixture containing NO₂ (200 ppm), CO (200 ppm), O₂ (12%), CO₂ (14%) with the balance N₂ at a flow rate of 2 liters per minute was passed over the non-metallised zeolite (0.4 g) from room temperature to 400° C. at a heating rate of 50° C. per minute. In a subsequent experiment, the catalyst temperature was first raised to 250° C. and 200 ppm NH₃ was added to the gas stream, the zeolite was exposed to that stream for 5 minutes and then the NH₃ was switched off, and the catalyst was cooled to room temperature and the rapid light-off repeated. FIG. 9 shows the outlet NOx concentration from these experiments. It can be seen that in the absence of pre-adsorbed NH₃, NO₂ is adsorbed at low temperature over the zeolite and is released between 100° C. and 300° C., but when NH₃ was pre-adsorbed on the catalyst, significant NOx reduction is shown over the entire temperature window up to 400° C.

We have also shown that even in the presence of hydrocarbon, H₂O and SO₂ adsorbed NH₃ will readily react with NO₂. FIG. 10 shows the effect of adding C₃H₆ on the reaction of pre-adsorbed NH₃ with NOx, and FIG. 11 demonstrates the effect with addition of H₂O and SO₂.

EXAMPLE 3 Reaction of NO₂ With Pre-adsorbed NH₃ Over Non-metallised ZSM5 in Cycle Test

In most cases, exhaust gas temperature varies during an engine cycle and for a significant fraction of that time the temperature can be low. We have shown that by injecting NH₃ over a set temperature during the cycle, the adsorbed NH₃ can subsequently be utilised in reducing NOx at both low and high temperature. In the experiment, exhaust gas containing CO₂ (14%), O₂ (12%), H₂O (10%), CO (200 ppm), C₃H₆ (200 ppm), SO₂ (20 ppm) and NO₂ (200 ppm) was cycled between 150° C. and 350° C. with a dwell of approximately 5 minutes at 250° C. during the cooling-down part of the cycle. The NH₃ injection was switched on when the temperature was at 350° C. and switched off when the temperature fell to 250° C. FIG. 12 shows the outlet NOx concentration and the temperature against time without any NH₃ injection, and FIG. 13 shows the effect of the cycling with the intermittent injection of NH₃. In both Figures, the ordinate scale gives the degrees C for the temperature graph and the parts per million (ppm) for the NOx graph.

EXAMPLE 4 Reaction of NO With Pre-adsorbed NH₃ Over Cu/ZSM5

This Example shows the effect of pre-adsorbing NH₃ at 250° C. on the conversion of NOx over a Cu-impregnated ZSM5 (containing 5% copper by weight) in a simple gas mixture containing NOx, CO, CO₂ and O₂ during a light-off test from room temperature to 400° C. The gas stream containing NO (200 ppm), CO (200 ppm), O₂ (12%), CO₂ (14%) with the balance N₂ at a flow rate of 2 liters per minute was first passed over the Cu/ZSM5 (0.4 g) from room temperature to 400° C. at a heating rate of 50° C. per minute and the NOx at the outlet measured. In a subsequent experiment, the catalyst temperature was first raised to 250° C. and 200 ppm NH₃ was added to the gas stream, the Cu/ZSM5 was exposed to that stream for 5 minutes and then the NH₃ was switched off, the catalyst was cooled to room temperature rapidly and the light-off repeated. FIG. 14 shows the outlet NOx concentration for these experiments. It can be seen that in the case where NH₃ was not pre-adsorbed on the catalyst, some of the NOx is adsorbed on the zeolite at low temperature, and is then subsequently released at higher temperature, but the pre-adsorption of NH₃ at 250° C. suppresses the amount of NOx adsorbed at low temperature, with significant NOx reduction by the pre-adsorbed NH₃ at temperatures greater than 125° C.

Similarly, even in the presence of other gaseous components such as hydrocarbon, H₂O and SO₂ the adsorption of NH₃ will occur readily over the Cu/ZSM5 and can be used to reduce NOx. For example, FIG. 15 shows the effect of pre-adsorbing NH₃ on the Cu/ZSM5 at 250° C. from a gas mixture containing NO, H₂O, CO₂, CO, C₃H₆, SO₂ and O₂ and the reduction of NOx by the adsorbed NH₃ during a light-off test. 

What is claimed is:
 1. A method of reducing the content of nitrogen oxides (NOx) in the exhaust gas of a diesel engine operating in a substantially continuously lean burn mode, which method comprises: passing the exhaust gases over a selective catalytic reduction catalyst comprising zeolite which both releasably adsorbs ammonia and catalyses the reduction of NOx to nitrogen by ammonia during an engine cycle; supplying ammonia to the catalyst during the engine cycle from a source of ammonia, when the catalyst temperature is above a first pre-determined temperature; adsorbing ammonia to the catalyst during ammonia supply; discontinuing the ammonia supply when the catalyst is below a second pre-determined temperature; and reacting ammonia absorbed on the catalyst with NOx when the catalyst is below a second pre-determined temperature.
 2. A method according to claim 1 wherein the zeolite is ZSM-5.
 3. A method according to claim 1 wherein the zeolite catalyst is non-metallised.
 4. A method according to claim 1 wherein the zeolite contains a metal.
 5. A method according to claim 4 wherein the metal is selected from the group consisting of copper, iron, cerium and platinum.
 6. A method according to claim 1 wherein the metal is Cu/ZSM-5.
 7. A method according to claim 1 wherein the first pre-determined temperature is in the range of about 250-400° C. and the second pre-determined level is in the range of about 200-250° C.
 8. An apparatus for reducing the content of nitrogen oxides (NOx) in the exhaust gas of a diesel engine operating in a substantially continuously lean burn mode comprising: (a) an exhaust apparatus capable of allowing exhaust gas to flow therethrough; (b) a selective catalytic reduction catalyst comprising zeolite located in the flow-path of the exhaust gas and being capable of both catalyzing the reduction of NOx in the exhaust gas to nitrogen and releasably adsorbing ammonia during the engine cycle; (c) means for supplying ammonia from an ammonia source to the catalyst; and (d) switching means for controlling the supply of ammonia during an engine cycle such that ammonia supply is switched on when the catalyst temperature rises above a first pre-determined temperature at which ammonia is adsorbed on the catalyst and the ammonia supply is switched off when the catalyst temperature falls below a second pre-determined temperature, whereby adsorbed ammonia is available to react with NOx when the catalyst is below the first pre-determined temperature.
 9. An apparatus according to claim 8, wherein the first pre-determined temperature is in the range of about 250-400° C. and the second pre-determined temperature is in the range of about 200-250° C.
 10. An apparatus according to claim 8 wherein the zeolite catalyst is ZSM-5.
 11. An apparatus according claim 8 wherein the zeolite catalyst is non-metallised.
 12. An apparatus according to claim 8 wherein the zeolite contains a metal.
 13. An apparatus according to claim 12 wherein the metal is selected from the group consisting of copper, iron, cerium and platinum.
 14. An apparatus of claim 12 wherein the metal is Cu/ZSM-5. 